Real and lab reactors
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1 Real and lab reactors
2 New HDS (hydrodesulfurizer) Unit, ARCO Carson, CA Refinery
3 Fluid Cat Cracker (Chevron) Stacked Fluid Cat Cracker (UOP)
4 Shell Cat-Cracker All-riser Cracking FCC Unit
5 10/30 female joint 10/30 male joint 9 mm O-ring joint 4 ft. preheater coil of 2 mm capillary tubing 7" Thermocouple guide of 2mm capillary tubing Laboratory Pyrex FBR (fluidized bed) reactor. Catalyst space Fritted disc
6 Product Steam stripping Flue gas Transferline reactor Fluid-bed regenerator Feed Air Transfer line Design of typical FCC transfer-line (riser) reactor with fluidized-bed regenerator: lab version of the big refinery reactors.
7 Table 12.1 Classification of Catalytic Reactors Basis for Classification Classes Examples Size Laboratory 0.5 cm diam. tubular microreactor (0.1-1 g catalyst) Bench scale 2.5 cm diam. x cm long tubular reactor ( g catalyst) Pilot scale 7.5 cm diam x 6-10 m long tubular reactor ( kg catalyst) Plant scale 1-6 m diam x m long tubular reactor ( metric tons cat.) Methods of charging and discharging Batch Stirred liquid and solids Flow, steady state a. tubular, fixed catalyst bed b. slurry, mixed fluid, mixed solids Motion of catalyst particles relative to each other Fixed Tubular fixed solids (fixed bed) Relative motion a. fluidized bed b. slurry bubble column Fluid flow Tubular, plug flow Turbulent gas in tubular fixed bed Slurry reactor with mechanical
8 Hardware and Software Scientific & Engineering Tasks Scientific & Engineering Disciplines Discover Reaction C. Reactor/process design perspective Laboratory Reactor Intrinsic Kinetics Catalyst Prop. Diff., Mass Trans Chemical Kinetics and Catalysis Kinetic Model Development Reaction Engineering & Mathematics Rate/Selectivity & Rate Equation Reactor Model Development Reactor Model Fig Structure of Catalytic Process Development [adapted from J. M. Smith, Chem. Eng. Prog., 64, 78 (1968)]. Reactor /Process Design Catalytic Reactor Design Pilot Plant Reactor Process Design Economics Finl. Plant Design & Economic Studies Large Scale Plant
9 II. Common Lab and Bench Scale Reactors fixed bed tubular stirred gas, fixed bed stirred liquid/gas, stirred catalyst fluid bed fixed bed, transient gas flow Laboratory and bench-scale reactors vary greatly in size, complexity, cost, and application.
10 Gas-Liquid CSTR (UCSB) Batch Reactor (UCSB)
11 Bench scale reactor (courtesy of Shell Corp.)
12 Seven Criteria for Selection of Laboratory and Bench-Scale Catalytic Reactors Criterion Issues Involved/Measures of/methods to Meet Criterion 1. Satisfy purpose of measurement (i.e., application) Measure: (1) intrinsic activity/selectivity, (2) kinetics of reaction and deactivation Obtain mechanistic understanding Simulate process 2. Avoid catalyst deactivation where possible; where not, decide if fast or slow See Chap. 5 (B&F) on avoiding different kinds of catalyst deactivation Fast decay causes activity and selectivity disguises and requires use of transient or transport reactor Slow decay best studied using CSTR or differential reactor 3. Avoid inter- and intra-particle heat and mass transport limitations Thiele modulus less than 0.5; small particles or thin catalyst layer Minimize film thickness with high flow rates, turbulence Operate at low conversions Use CSTR or differential reactor 4. Minimize temperature and concentration gradients Gradients cause activity and selectivity disguises Maximize mixing in batch reactor and CSTR; use inerts Use CSTR or differential reactor where possible 5. Maintain ideal flow patterns Minimize mixing and laminar flow in tubular reactors; Maximize mixing and minimize gradients in CSTR Avoid gas or liquid holdup in multi-phase reaction systems
13
14 Reactor cooling is very size dependent Elephants have a serious cooling problem, mice don t
15 Distribution of unreacted material CA and temperature in a packed bed reactor.
16 Most tubular reactors are filled with catalyst and are called packed bed reactors. In this case we probably can assume that most of the heat flow is by conduction with little convection and radiation because the space is full of solid particles. In this plot across a reactor with cooled walls, the temperature is highest and the conversion lowest along the center. (This is for a reversible exothermic reaction where the heat shifts the equilibrium) This obviously depends on reversible/irreversible, endothermic/exothermic.
17 Cooling systems for PFTR s, countercurrent is best in principle because it cools the hot end of the reaction and warms the cold end. However, it may lead to a hot-spot near the start of the tube. Hot spots are a major problem for PFTR s. 17
18 Another approach is to use the outgoing mix to warm the incoming reactants. The temperatures can go above adiabatic because the reaction heat is being cycled back into the feed.
19
20 Lab scale plug flow reactor: note the fine coils inside the temperature jacket.
21 Where is the chemical industry going? Could it be decentralized? Central Local Steel Beer Electronics X X Cars X Fuels Plastics X Chemicals Declining?? From gas? Small parts 3DP Computing Information
22 Corporate Strategy Select Between Business Units Boston Consulting Group
23 Microreactors
24 Bench scale achieved desired conversion, yield, selectivity, productivity Scale-up Alternatives: 1. Scale-up in parallel (Scale-out, scale-up by multiplication.) 2. Scale-up vertically account for effect of change in equipment scale on multi-scale interaction of transport and kinetic phenomena. S2 S7 CHEMICAL REACTION ENGINEERING LABORATORY Commercial production
25 SOME KEY SCALE-UP REQUIREMENTS Match mean residence time or mean contact time Match [or account for the change in] dimensionless variance of residence ( contact) times Match [or account for change in] covariance of sojourn times in different environments (phases) of the system Match heat transfer per unit volume, or account for the change with change in scale of equipment
26 Direct Scale-up of Tubular and Packed Bed Wall-Cooled Reactors: Scale-up by Multiplication Single tube of diameter dt and length L at given feed conditions (Po, To, Co) and given feed rate Q (l/h), produces the desired product at the rate of (mol P/h) and the desired selectivity. S Identical tubes of diameter dt and length L produce then the commercial production rate FpC (S = FpC ( ), using identical feed conditions and flow rate, at the desired selectivity. Possible Problems:- External heat transfer coefficient - Flow manifold for flow distribution SAME PRINCIPLE USED IN MICROREACTORS
27 Advantages of Micro reactors High surface-to-volume area; enhanced mass and heat transfer; high volumetric productivity; Laminar flow conditions; low pressure drop Residence time distribution and extent of back mixing controlled Low manufacturing, operating, and maintenance costs, and low power consumption Minimal environmental hazards and increased safety due to small volume Scaling-out or numbering-up instead of scaling-up S2 S9 CHEMICAL REACTION ENGINEERING LABORATORY
28 Small Scale Production
29 Small scale production up to 100 kg/h fits in fume-cupboard completely automated production flexibility
30 Scaling Out Micro reactors Single channel 10 Multi-channel design Scale-out g g ton Slug 1 churn bubbly jl (m/s) Flow regimes, Interfacial area Mass transfer slug wavy annular Heatexchangers annular Annular Reactors j G (m/s) 100 Uniform flow distribution and nature of contacting pattern Methods for design of multi-phase reactors Integrated sensors for gas-liquid flows N. de Mas, et al., Ind. Eng. Chem Research, 42(4); (2003)
31 Disadvantages of Micro Reactors: Short residence times require fast reactions Fast reactions require very active catalysts that are stable (The two most often do not go together) Catalyst deactivation and frequent reactor repacking or reactivation Fouling and clogging of channels Leaks between channels Malfunctioning of distributors Reliability for long time on stream Challenge of overcoming inertia of the industry to embrace new technology for old processes Most likely implementation of micro-reactors in the near term: Consumer products Distributed small power systems Healthcare In situ preparation of hazardous and explosive chemicals
32 Other weird reactors
33 Silica Synthesis: Laminar Flow Reactor dm (nm) Khan, et al., Langmuir (2004), 20, µm (%) t (min) Wide particle size distribution (PSD) at low residence times Particle growth is fastest, and hence most sensitive to residence time variations PSD at high residence times approaches batch synthesis results (8% vs. 5%) Pratsinis, Dudukovic,Friedlander, CES(1986) effect of RTD on size pdf
34 Silica Synthesis: Segmented Flow Reactor (%) Batch SFR LFR Gas Gas 1 µm SFR enables continuous synthesis with results that mirror those obtained from batch synthesis Khan, et al., Langmuir (2004), 20, 8604
35 Plasma or laser reactors Superior Micropowders Abq
36 Highly compact heat exchangers The basis of HEX-reactors, with catalysts on each side. Hundreds of channels, each needing identical feeds here for hydrogen production.
37 Ceramic micro-heat exchanger Basis of high temperature reactions still fabrication problems. Scale in cm.
38 Spinning disc reactor Rotation to 10,000 rpm; used for food processing & chemical reactions. Needs to deal with very rapid exo- or endothermic processes on the top surface.
39 SDR Wave formation strong mixing in a thin film
40 SDR Temperature distribution Uniform/isothermal heating of treacle!
41 Thermal control on an SDR Overall U of 10 kw/sq.m.k transfers 39 kw from a 0.5 m diameter disc with a 20 K temperature difference, even for organic fluids.
42 Custard manufacture Milk & custard powder are introduced onto the centre of the SDR continuous production is feasible.
43 Membrane Reactors Membrane reactors can be used to achieve conversions greater than the original equilibrium value. These higher conversions are the result of Le Chatelier s principle; you can remove the reaction products and drive the reaction to the right. To accomplish this, a membrane that is permeable to that reaction product, but impermeable to all other species, is placed around the reacting mixture. 43
44 Membrane Reactors Example: The following reaction is to be carried out isothermally in a membrane reactor with no pressure drop. The membrane is permeable to product C, but impermeable to all other species. Inert Sweep Gas C6 H12 C6 H 6 3H 2 C H (A) 6 12 A B 3C Inert Sweep Gas 44 H2 (C) C6H6 (B) Cyclohexane to cyclohexene or to benzene. Membrane can be palladium which is permeable only to hydrogen. Much researched but not commercial.
45 Membrane selectivity Most polymers are permeable to gases depending on solubility of the gas in the polymer and diffusivity of the gas. Solubility is very variable depending on chemical compatibility. Diffusivity mostly depends on molecular size. CO2/O2 selection is quite feasible, O2/N2 selectivity is not very good. Cellulose and related membranes can be permeable to water but not salts. Used for reverse osmosis and kidney dialysis. There are commercial biochemical membrane reactors but not real chemical membrane reactors.
46 Toshiba mobile phone 100 mw direct methanol fuel cell (2005) where micro heat exchanger/reactor technology is needed.
47 A laptop like the earlier mobile phone! The chip still needs cooling, as well as the thermal control of the fuel cell reformer. The methanol supply is shown temporarily fitted to the laptop. (NEC)
48 Alternatives to heat Photochemical reactors Microwave reactors Enzymic reactors Electrochemical processes Fermentation
49 Last
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